Process for the preparation of phenol and cyclohexanone which comprises: a. the synthesis of cyclohexylbenzene by the hydro-alkylation of benzene by contact with hydrogen or the alkylation of benzene with cyclohexene using Y zeolites; b. the selective aerobic oxidation of cyclohexylbenzene to the corresponding hydroperoxide catalyzed by N-hydroxy-derivatives in the presence of polar solvents; and c. the scission of the hydroperoxide of cyclohexylbenzene to phenol and cyclohexanone by homogeneous or heterogeneous acid catalysts; characterized in that the synthesis of cyclohexylbenzene takes place in the presence of a catalytic system comprising a Y zeolite and an inorganic ligand wherein the Y zeolite has a crystalline structure with openings consisting of 12 tetrahedra and the inorganic ligand is -alumina, and wherein said catalytic composition is characterized by a pore volume, obtained by adding the mesoporosity and macroporosity fractions, greater than or equal to 0.7 cm3/g, wherein at least 30% of said volume consists of pores with a diameter greater than 100 nanometers.